:عجرملا
Project Title - )يبنجأو يبرع( عورشملا ناونع
فتاهلا مقر
Telephone
ينورتكللاا ناونعلا e-mail
03-765702 hanafyholail@bau.edu.lb
ناونعلا
Address
ةيبدلا
Principal Investigator -
يسيئر لا ثحابلا
ةيفيظولا ةسسؤملا مسلاا
Post
ةيلك ديمع
مولعلا
Institution
ةعماج
توري ب
ةي برع لا
Name
ليله يفنح .د.أ
ينورتكللاا ناونعلا e-mail hhammud@yahoo.com
Co-Workers -
ن وكراشملا نوثحابلا
ةسسؤملا مسلاا
Institution
توري ب ةع ماج
ةي برع لا
Name
2 years
:
Duration -
عورشملل ةيدقاعتلا ةدملا

The aim of the project was to study the feasibility of water treatment of dyes pollutants using low cost and highly available biomass green algae.
The use of dried algae for the removal of Toxic dyes from its aqueous solution is a good method for treatment of wastewater. Biosorption exploits the ability of plant biomass to sequester solute particles from aqueous solution by physiochemical mechanisms. Marine algae have been reported to have high metal binding capacities due to the presence of polysaccharides, proteins or lipid on the cell wall surface containing functional groups such as amino, hydroxyl, carboxyl and sulphate, which can act as binding sites for metals.
We will test the ability of brown marine algae Carolina sp . to remove different kind of dye such as methylene blue (MB); and crystal violet (CV).
In this view the following steps are undertaken:

Optimize the uptakes conditions (pH, temperature, contact time,).

Determination of the order of the adsorption.

Determination of the thermodynamic parameters.

Determination of the isotherm adsorption parameters.

Use of algae, as industrial and environmental applications, to clean waste water from dyes.

Use some chemical compounds to modify the surface of the brown algae.

Use the column to study the sorption/desorption of dyes by the biomass.
1.
Water quality studies:
Litani region water sampling and analysis was achieved in the summer and winter seasons. The data was documented in the (first year report).
2.
The treatment of dyes using marine algae was achieved in three case studies for both batch experiments (first year report) and column experiments: a.
Biosorption of Organic Dyes Methylene blue (MB) by Green Marine Algae
Enteromorpha spp:
T his study evaluates the biosorption capacity of the highly available, low cost and renewable green alga Enteromorpha . The effects of contact time, pH on the sorption behavior were investigated. The biosorbents studied are enteromorpha algae and its modified forms. The

modification was successfully carried out using CaCl
2
and formaldehayde.
FT-IR and thermal analysis of pure algae and algae material after modification and methylene blue uptake are compared for characterization purpose
Several equilibrium models (Langmuir and Freundlich) were tested after both linear and non-linear regression analysis in order to fit the experimental data and to understand the possible physiochemical interactions involved in the sorption phenomenon between the algae surface (modified and non modified) and the dye molecules.
The capacity of removal of methylene blue by Enteromorpha algae was found to range from 950 to 970 mg/g.
The thermodynamics of biosorption were calculated and discussed. Also the rate of biosorption for the removal of methylene blue was studied and was found to obey second order kinetic.
In addition to column study for the Enteromorpha sp.
green marine algae was carried out.
The breakthrough curves and the percentage efficiency showed the behavior of the three successive sorption/desorption cycles of both Modified algae and raw algae. The column study proves that high efficiency of removing dye is attained.
Biosorption of organic dyes by Brown Marine Algae Carolina
The general methods and materials used in this study were described. Agitation removal of methylene blue by Carolina algae was undertaken. Also the optimum conditions (pH, mass of algae,..) for this adsorption reaction were determined. The kinetic study showed fitting of pseudo-second order kinetic models. The results of isothermal study indicates fitting of
Langmuir model for the linear regression analysis and both Langmuir and Redlich-Peterson isotherm models for the non-linear regression analysis. The maximum adsorption capacity of methylene blue was estimated as 55 mg/g at 19 °C, and the percentage remove was 85%. The negative values of enthalpy, entropy and Gibbs free energy revealed that adsorption process is exothermic, ordered and spontaneous.
The removal of methylene blue by chemically modified Carolina brown marine algae is described. The raw algae were modified with NaOH, CaCl
2
and formaldehyde. The results of the isothermal study showed that the experimental adsorption data fitted well with Langmuir model and the uptake increased about 18 % by using the formaldehyde modified algae. This can be explained by the fact that the binding sites are increased at the surface of the biomass. The kinetic study showed that the adsorption rate follows a pseudo-second order. The rate constant

increased upon modification of algae, it is greatest for NaOH modified algae.
Column study for the Carolina brown marine algae and its three kind of modified form is presented. Three sorption-desorption cycles were operated for the modified brown algae
(with NaOH, CaCl
2
, and formaldehyde). The breakthrough curves showed the behavior of the three successive sorption/desorption cycles. The percentage efficiency is about 100 % in the first cycle. About 90 % of elution happened in the first aliquot of desorbed solution during the regeneration treatment. The uptake of dye decreased with the increase in the cycle number for the three modified algae. c.
Biosorption of Organic Dye Crystal Violet by Red Marine Algae Jania:
Biosorption, a new low cost technology has been studied for the removal of crystal violet and lead using marine red algae Jania sp.
and its chemically modified forms. The study covers the removal of crystal violet by the raw and chemically modified red marine algae Jania sp.
using agitation and soaking method. Also the optimum conditions for this adsorption reaction were determined. The red alga Jania rubens which is widely distributed in the Mediterranean
Sea was used to prepare an alternative low cost biosorbent to remove crystal violet from aqueous solutions under equilibrium experimental conditions. Different pre-treatments: chemical cross-linking with CaCl
2
or H
2
CO, have been tested in order to improve the stability as well as the adsorption capacity of the algal biomass. The adsorption capacity of the biosorbent was investigated as a function of temperature, contact time and initial concentration of adsorbate. The high uptake value of at 30 °C: 1114 mg/g, 521mg/g and 499 mg/g respectively for raw Jania algae, modified Jania algae with formaldehyde and modified Jania algae with calcium chloride let us suggest that it is a promoting adsorbent for wastewater treatment. The adsorption behavior can be described as Chemisorption for raw Jania algae and modified Jania algae with formaldehyde and described as Physiosorption for modified Jania algae with calcium chloride. The kinetic study indicates that adsorption rate follows a pseudosecond order for the adsorption of Crystal Violet onto raw Jania algae and modified Jania algae with formaldehyde, while it follows a pseudo-first order for modified Jania alage with calcium chloride. The negatives values of standard free energy for all form of Jania studied indicate that adsorption of CV is a favorable process (spontaneous). The standard enthalpy is positive for all form of Jania indicates that the adsorption is endothermic. In conclusion, Jania algae and its modified forms are promising sorbent materials for dye removal.
Column studies is described in chapter is about the study of the removal of crystal violet by the

raw and chemically modified red marine algae Jania sp.
using biosorption column. The regenerative biosorption system with Jania sp and the modified Jania with formaldehyde appear feasible under relatively simple conditions adopted in the present work.
The present research has an important outcome in reducing environmental pollution by treating
water using biosorption techniques. The sorbent used is a ready available and low cost algae and chemically modified for longer preservation and improving uptake. The pollutant being organic dyes. Batch experiment proved that high removal capacity of dye has been obtained up to 1000 mg/g, while column experiment (sorption and desorption) proved that industrial application is possible with longer lifetime of column.
-
Conferences:
1.
Hanafy Holail, Hassan Hammud, Rajaa Fakhoury, and Mahmoud Halablab , Water
Quality of Litani River in Lebanon, The 15
Th
Interdisciplinary Conference on the
2.
Environment , July 8-11, 2009, The Interdisciplinary Environmental Association, Daytona
Beach, Florida, USA.
Mohammad Hanbali, Hanafy Holail, Hassan Hammud, De-pollution of Organic Dyes by
3.
Red Marine Algae and its modified forms , ReSooK Emuni Multi-conference proceeding ,
21 march 2011 Beirut, Lebanon.
Hawraa Zahrddin, Hanafy Holail, Hassan Hammud, Biosorption of Methylene Blue By
4.
Green Marine Algae , ReSooK Emuni Multi-conference proceeding , 21 march 2011
Beirut, Lebanon.
Lina Fayyoumi, Hassan Hammud, Hanafy Holail, Bassem El Hamaoui , Multiple sorption-desorption cycles of Methylene Blue in A fixed-bed column by modified brown marine algae, ReSooK Emuni Multi-conference proceeding , 21 march 2011 Beirut,
Lebanon.
Publications :

1.
Hassan Hammud, Lina Fayoumi, Hanafy Holail , El-Sayed M.E. Mostafa, “ Biosorption studies of methylene blue by Mediterranean algae Carolina and its chemically modified forms . Linear and nonlinear models’ prediction based on statistical error calculation” ,
International J chemistry. Vol. 3, No. 4 (2011) 147-163.
2.
Hassan Hammud, Lina Fayoumi, Hanafy Holail, Column and kinetic study for the removal of methylene blue by brown marine algae (Carolina sp.)and its modified form , under submission .
Thesis:
1.
Lina Fayoumi, Biosorption of organic dyes by Marine Algae , Master Thesis (Chemistry),
Suprvisor: Hanafy Holail, Hassan Hammud, Beirut Arab University, June 2011.
2.
Hawraa Zahreddin, Biosorption of Organic Dyes and Heavy Metals by Green Marine
Algae , Master Thesis (Biology), Suprvisor: Hanafy Holail, Hassan Hammud, Beirut
Arab University, April 2012.
3.
Mohammad Hanbali
,
Biosorption of Organic Dyes and Heavy Metals by Red Marine
Algae , Master Thesis (Biochemistry), Suprvisor: Hanafy Holail, Hassan Hammud,
Beirut Arab University, April 2012.
The present work deals with the adsorption of methylene blue (MB) and crystal violet
(CV) by Enteromorpha sp.
, Jania and Carolina algae which are widely spread on
Mediterranean coast of Beirut. For this reason, algae would constitute an ideal material to be used as biosorbent. In addition, to the best of our knowledge, studies of dye adsorption by modified algae are not available; therefore, exploring this promising field of biosorption is desirable.
The term biosorption refers to different modes involving a combination of active and passive transport mechanism to remove unwanted materials by microbial biomass. Binding to sites at the cell surface which exhibit chemical affinity for the adsorbate, is generally nonmetabolism dependent and so occurs for both viable and inactive microbial cells.
In order to perform the adsorption experiments, different pre-treatments for the chemical modification of the biomass, among them treatment with NaOH, CaCl
2 and chemical crosslinking wit formaldehyde, have been tested to improve its stability as well as its adsorption

capacity, making it suitable for industrial use.
FT-IR and thermal analysis of pure algae and algae material after modification and dyes uptake are compared for characterization purpose. The biosorption process has been analyzed through batch experiments at different temperatures with regard to the influence of the initial dye concentration and the effect of shaking and contact time. The high removal capacity of dyes by algae has been obtained up to 1000 mg/g is a very promising results.
This work also includes column application regarding algae aiming to evaluate the breakthrough curve. The excellent result obtained opens the path for industrial application.
Finally, isothermal kinetic studies for dyes sorption on algae and its modified forms was developed in order to explain the adsorption behavior and the different effects studied on the dye uptake.